The present invention relates to a retardation film having a smaller retardation value at a shorter wavelength at a measuring wavelength of 400-700 nm, that is used in optical elements of liquid crystal display devices, anti-glare films, optical recording devices and the like, and to circular polarizing plates, elliptical polarizing plates, liquid crystal display devices and other optical devices.
Retardation films are used in STN (Super Twisted Nematic) systems of liquid crystal display devices and the like, and they are employed to solve such problems as color compensation and to achieve viewing angle widening. The materials generally used in retardation films for color compensation are polycarbonates, polyvinyl alcohol, polysulfone, polyethersulfone, amorphous polyolefins and the like, while the materials used in retardation films for viewing angle widening are those mentioned above, as well as polymer liquid crystals, discotic liquid crystals, and the like.
A quarter-wave plate, which is one type of retardation film, can convert circularly polarized light to linearly polarized light, or linearly polarized light to circularly polarized light. This has been utilized in liquid crystal display devices and, particularly, in reflective liquid crystal display devices having a single polarizing plate where the rear electrode, as viewed by an observer, is the reflecting electrode, in anti-reflection films comprising a combination of a polarizing plate and a quarter-wave plate, or in combination with reflective polarizing plates composed of cholesteric liquid crystals or the like that reflect only circularly polarized light only in either the clockwise direction or counter-clockwise direction.
The retardation films used in the aforementioned single polarizing plate-type reflective liquid crystal display devices and reflective polarizing plates must have a function of converting linearly polarized light to circularly polarized light and circularly polarized light to linearly polarized light, in the visible light region with a measuring wavelength of 400-700 nm, and preferably 400-780 nm. When this is accomplished with a single retardation film, the retardation film ideally has a retardation of xcex/4 (nm) at a measuring wavelength xcex of 400-700 nm, and preferably 400-780 nm.
Although the aforementioned color compensating retardation film materials are commonly used as quarter-wave plates, these materials exhibit birefringent wavelength dispersion. The birefringence of most polymer films becomes larger as the measuring wavelength becomes shorter, and becomes smaller at longer wavelengths. Consequently, with a single polymer film it has been difficult to achieve a smaller birefringence at shorter measuring wavelengths at a measuring wavelength xcex of 400-700 nm, such as with the aforementioned ideal quarter-wave plate.
In order to achieve a smaller birefringence with shorter measuring wavelengths as with an ideal quarter-wave plate, Japanese Unexamined Patent Publication HEI No. 10-68816 has disclosed a technique of using a quarter-wave plate and a half-wave plate attached together at an appropriate angle, and Japanese Unexamined Patent Publication HEI No. 2-285304 has disclosed a technique whereby two retardation films with different Abbe numbers are laminated.
Current techniques require the use of two films in order to achieve a film with a smaller retardation with shorter measuring wavelengths as with ideal quarter-wave plates, and this has presented problems such as additional steps for film attachment and increased costs as well as greater expense for the optical design. In Japanese Unexamined Patent Publication HEI No. 3-29921 there is disclosed a retardation film obtained by uniaxially stretching a film composed of a mixture or copolymer of at least two different organic polymers, wherein the first organic polymer of the two different organic polymers has a positive photoelastic constant and the second organic polymer has a negative photoelastic constant, so that the retardation film has a larger birefringence at shorter measuring wavelengths; however, no reference is made to a method of reducing the birefringence at shorter measuring wavelengths. The present invention solves this problem by allowing realization of a retardation film with a smaller retardation, at shorter measuring wavelengths, using a single film.
The present inventors have diligently researched polymer materials for retardation films with the aim of solving the aforementioned problem, and have succeeded in providing a retardation film comprised of a single oriented polymer film, characterized in that the retardation at wavelengths of 450 nm and 550 nm satisfies the following formulae (1) and/or (2):
R(450)/R(550) less than 1xe2x80x83xe2x80x83(1)
K(450)/K(550) less than 1xe2x80x83xe2x80x83(2)
where R(450) and R(550) represent the in-plane retardation of the oriented polymer film at wavelengths of 450 nm and 550 nm, respectively, and K(450) and K(550) are the values calculated by K=[nzxe2x88x92(nx+ny)/2]xc3x97d (where nx, ny and nz represent the three-dimensional refractive indexes of the oriented polymer film as the refractive indexes in the direction of the x-axis, y-axis and z-axis, respectively, and d represents the thickness of the film) for the oriented polymer film at a wavelength of 450 nm and 550 nm, respectively, and the water absorption is no greater than 1%.
[1] A retardation film comprising a single oriented polymer film, the retardation film being characterized in that the retardation at wavelengths of 450 nm and 550 nm satisfies the following formulae (1) and/or (2), and the water absorption is no greater than 1%.
R(450)/R(550) less than 1xe2x80x83xe2x80x83(1)
K(450)/K(550) less than 1xe2x80x83xe2x80x83(2)
(where R(450) and R(550) represent the in-plane retardation of the oriented polymer film at wavelengths of 450 nm and 550 nm, respectively, and K(450) and K(550) are the values calculated by K=[nzxe2x88x92(nx+ny)/2]xc3x97d (where nx, ny and n represent the three-dimensional refractive indexes of the oriented polymer film as the refractive indexes in the direction of the x-axis, y-axis and z-axis, respectively, and d represents the thickness of the film) for the oriented polymer film at a wavelength of 450 nm and 550 nm, respectively.]
[2] A retardation film according to [1], wherein the retardation at wavelengths of 450 nm, 550 nm and 650 nm satisfies the following formulae (3) and (4):
0.6  less than R(450)/R(550) less than 0.97xe2x80x83xe2x80x83(3)
1.01  less than R(650)/R(550) less than 1.4xe2x80x83xe2x80x83(4)
where R(650) represents the in-plane retardation of the oriented polymer film at a wavelength of 650 nm.
[3] A retardation film according to [1] or [2], wherein the retardation is smaller with a shorter wavelength in the wavelength range of 400-700 nm.
[4] A retardation film according to [1] to [3], which comprises an oriented polymer film wherein
(1) the film is composed of a polymer comprising a monomer unit of a polymer with positive refractive index anisotropy (hereunder referred to as xe2x80x9cfirst monomer unitxe2x80x9d) and a monomer unit of a polymer with negative refractive index anisotropy (hereunder referred to as xe2x80x9csecond monomer unitxe2x80x9d),
(2) R(450)/R(550) for the polymer based on the first monomer unit is smaller than R(450)/R(550) for the polymer based on the second monomer unit, and
(3) the film has positive refractive index anisotropy.
[5] A retardation film according to [1] to [3], which comprises an oriented polymer film wherein
(1) the film is composed of a polymer comprising a monomer unit that forms a polymer with positive refractive index anisotropy (hereunder referred to as xe2x80x9cfirst monomer unitxe2x80x9d) and a monomer unit that forms a polymer with negative refractive index anisotropy (hereunder referred to as xe2x80x9csecond monomer unitxe2x80x9d),
(2) R(450)/R(550) for the polymer based on the first monomer unit is larger than R(450)/R(550) for the polymer based on the second monomer unit, and
(3) the film has negative refractive index anisotropy.
[6] A retardation film according to [1] to [5], wherein the oriented polymer film is a thermoplastic resin with a glass transition temperature of 120xc2x0 C. or higher.
[7] A retardation film according to [1] to [6], wherein the oriented polymer film contains a polycarbonate with a fluorene skeleton.
[8] A retardation film according to [1] to [7], which is an oriented polymer film comprising copolymer and/or blend of polycarbonates in which 30-90 mole percent of the total consists of a repeating unit represented by the following general formula (I): 
where R1-R8 are each independently selected from among hydrogen, halogen atoms and hydrocarbon groups of 1-6 carbon atoms, and X is 
xe2x80x83and 70-10 mole percent of the total consists of a repeating unit represented by the following general formula (II): 
where R9-R16 are each independently selected from among hydrogen, halogen atoms and hydrocarbon groups of 1-22 carbon atoms, and Y is 
xe2x80x83or xe2x80x94R23xe2x80x94,
wherein Y, R17-R19, R21 and R22 are each independently selected from among hydrogen, halogen atoms and hydrocarbon groups of 1-22 carbon atoms, R20 and R23 are selected from among hydrocarbon groups of 1-20 carbon atoms, and Ar is selected from among aryl groups of 6-10 carbon atoms.
[9] A retardation film according to [8], which is an oriented polymer film comprising copolymer and/or blend of polycarbonates in which 35-85 mole percent of the total consists of a repeating unit represented by the following general formula (III): 
where R24 and R25 are each independently selected from among hydrogen and methyl,
and 65-15 mole percent of the total consists of a repeating unit represented by the following general formula (IV): 
where R26 and R27, are each independently selected from among hydrogen and methyl,
and Z is selected from among 
[10] A retardation film according to [5], which is a blended oriented polymer film in which the polymer with positive refractive index anisotropy is poly(2,6-dimethyl-1,4-phenyleneoxide) and the polymer with negative refractive index anisotropy is polystyrene, wherein the polystyrene content is from 67 wt % to 75 wt %.
[11] A retardation film according to [1] to [10], wherein the b* value representing the object color is 1.3 or smaller.
[12] A retardation film according to [1] to [11], which is a xcex/4 plate.
[13] A retardation film according to [1] to [11], which is a xcex/2 plate.
[14] A retardation film according to [12] or [13], wherein R(550)xe2x89xa790 nm.
[15] A laminated retardation film prepared by laminating a xcex/4 plate and a xcex/2 plate, wherein both the xcex/4 plate and xcex/2 plate are a retardation film according to [1] to [14].
[16] A laminated retardation film according to [15), wherein the angle formed between the optical axes of the xcex/4 plate and xcex/2 plate is in the range of 50xc2x0-70xc2x0.
[17] A circular polarizing plate or elliptical polarizing plate prepared by laminating a polarizing plate with a retardation film according to [1] to [16].
[18] A circular polarizing plate or elliptical polarizing plate prepared by laminating a reflective polarizing plate with a retardation film according to [1] to [16].
[19] A circular polarizing plate or elliptical polarizing plate prepared by laminating a polarizing plate with a retardation film according to [1] to [16] and a reflective polarizing plate.
[20] A circular polarizing plate or elliptical polarizing plate according to [18] or [19], wherein the reflective polarizing plate has a function of reflecting only circularly polarized light rotated in one direction.
[21] A circular polarizing plate or elliptical polarizing plate according to [20], wherein the reflective polarizing plate is composed of a cholesteric liquid crystal polymer.
[22] A liquid crystal display device provided with a retardation film according to [1] to [21].
[23] A liquid crystal display device according to [22], which is a reflective liquid crystal display device.
[24] A liquid crystal display device according to [22] or [23], wherein the retardation film is a viewing angle compensating plate.
[25] A retardation film which is a retardation film comprised of a single polycarbonate oriented film, wherein the retardation at wavelengths of 450 nm and 550 nm satisfies the following formula (1):
R(450)/R(550) less than 1xe2x80x83xe2x80x83(1)
where R(450) and R(550) represent the in-plane retardation of the oriented polymer film at wavelengths of 450 nm and 550 nm, respectively, and R(550) is at least 50 nm.
[26] A reflective liquid crystal display device provided with a polarizing plate, a xcex/4 plate and a liquid crystal cell containing a liquid crystal layer between two substrates with transparent electrodes in that order, the reflective liquid crystal display device employing as the xcex/4 plate a retardation film comprising a single oriented polycarbonate film, wherein the retardation at wavelengths of 450 nm and 550 nm satisfies the following formula (1):
R(450)/R(550) less than 1xe2x80x83xe2x80x83(1)
where R(450) and R(550) represent the in-plane retardation of the oriented polymer film at wavelengths of 450 nm and 550 nm, respectively, and R(550) is 100-180 nm.